Process for dyeing wool



United States Patent 3,104,931 PRGCESS FOR DYEING WOOL Richard Casty, Kaiseraugst, Heinz Abel, Reinach, Arthur Maeder, Therwil, and Alfred Berger, Basel, Switzerland, assignors to Ciba Corporation, a corporation of Delaware N0 Drawing. Filed Mar. 9, 1959, Ser. No. 797,845 Claims priority, application Switzerland Mar. 11, 1958 Claims. (Cl. 8-54) This invention provides a process for dyeing wool, wherein the wool is treated in an aqueous medium with a :dyestufr which contains at least three sulfonic acid groups and is capable of entering into chemical combination with the fibers, and the treatment is carried out in the presence of a compound which contains at least one basic nitrogen atom to which is bound at least one radical containing a polyglycol ether chain, the molecule containing at least three groups and at least four carbon atoms not belonging to such group.

The process is also advantageous for dyeing wool in admixture with other nitrogenous fibers or fibers free from nitrogen.

The dyestuffs, with which the fibers are dyed, must contain at least one reactive group or reactive substituent. In other respects the dyestuffs may belong to a very wide variety of classes of dyestuffs, for example, stilbene dyestuffs, perinone dyestuffs, peri-dicarboxylic acid imide dyestufis, nitro dyestuffs, triphenylmethane dyestuffs, phthalocyanines and especially acid anthraquinone and azodyestuifs, including metal-free or metallizable or metalliferous monoor p0lyazo-dyestufis, the said dyestuffs containing groups or substituents capable of reacting with nitrogenous fibers. The dyestuffs also contain at least three sulfonic acid groups.

Among the aforesaid reactive groups or substituents there may be mentioned, for example, ethylene-imide groups, epoxy groups, or the vinyl group in .a vinylsulfone group or in the radical of acrylic acid, and especially labile substituents capable of splitting off easily with the taking over of the electron pair of the bond.

As labile substituents, which are capable of splitting OE With the taking over of the electron pair of the bond, there may be mentioned, for example, aliphatic-ally bound phosphoric or sulfuric acid ester groups, sulfonic acid fluoride groups, aliphatically bound sulfonyloxy groups and above all halogen atoms, especially a mobile chlorine atom. Advantageously the labile substituent is in the 'yor ii-position of an aliphatic radical Ibound directly or through an amino, sulfone or sulfonic acid amide group to the dyestufi' molecule. Tihose dyestuffs which contain halogen atoms as the labile substituents may contain these exchangeable halogen atoms in an aliphatic acyl radical, for example, in the ,B-position of a propionyl radical, or advantageously in a heterocyclic ring. the latter case there may be used dyestuffs which contain a monohalogenated heterocyclic ring, for example, a monochlorinated 1:3-:5-triazine radical, such as a 1:3:5- triazine radical of the formula in which X represents an alkyl, aryl, aralkyl, alkyl- 3, l 4,931 Patented Sept 24, 1963 ice mercapto or aryl-mencapto group, and especially an amino group which may be substituted or a hydroxyl group which is preferablysubstituted, or dyestuffs which contain a dichlorotriazine radical or a dichloropyrimidine radical.

A large number of dyestuffs of the above kind is known or can be made by methods in themselves known, for example, \from dyestuti components which contain the aforesaid labile substituents, or into which the labile substituents or radicals containing such labile substituents can be introduced by a method in itself known into the dyestulf after its manutacture. Thus, there are obtained :by reacting anthraquinone or azo dyestuffs which contain a reactive hydroxyl, mercapto or preferably -NH group, for example, with :chloracetylchloride, fi-bromo or fi-chloroapropionyl chloride or chloropropionic acid anhydri'de, or with cyanuric cholride or a primary vcyanunic chloride condensation product which contains two chlorine atoms and, instead of the third chlorine atom of the cyanuric chloride, an organic radical, valuable condensation products which contain an exchangeable chlorine atom and are suitable for dyeing by the process of this invention. The group of dyestufis to be used in the process, which contain a sulfonylated hydroxyl group can be made, for example, by reacting one molecular proportion of a :dyestufi which contains a hydroxyalkyl group, for example, a s-ulfonic acid N-hydroxyalkylamide group or a B-hydroxyalkyl-sulfonic acid, with at least one molecular proportion of an organic sulfonic acid halide, for example, paratoluene sul-fonic :aci-d chloride, benzene sulfonyl chloride or ethane sulfonyl chloride, or with concentrated sulfuric acid or chlorosultonic acid, in such manner that the hydroxyl group is acyl-ated.

The nitrogenous compounds in the presence of which the process is carried out contain at least one basic nitrogen atom to which is bound at least one radical containing a polyglycol ether chain. This chain consists of at least two I I -0o-ol 1 groups and may be bound directly or through -13. bridge member, for example, an alkylene radical, such as the radical CH CH CH to the nitrogen atom. The molecule of the nitrogen compound must contain at least three I I GC--O I I groups, advantageously CH --CH O-- groups.

Furthermore, the nitrogen compound must contain at least four carbon atoms not belonging to such a group. Thus, it advantageously also contains at least one aliphatic or alicyclic radical having at least 8 carbon atoms bound to one another, preferably an aliphatic radical having at least 12 carbon atoms bound to one another, and also an aromatic radical containing an aliphatic side chain and bound by an aryl carbon atom to the basic nitrogen atom.

It will be understood from the foregoing remarks that there are especially suitable as nitrogenous compounds of the above kind for use in the process reaction products of at least three molecular proportions of an a: fi-alkylene oxide with one molecular proportion of an organic compound which contains at least one basic primary or secondary amino group or a basic tertiary amino group, and also an alcoholic hydroxyl group, and salts or quaternary ammonium salts of these compounds.

As starting materials for making the aforesaid reaction products there may be used as azfi-alkylene oxides, ethylene oxide, propylene oxide or glycide. Especially valuable products are obtained from ethylene oxide.

As organic compounds, which contain at least one basic primary or secondary amino group or a basic tertiary amino group and also an alcoholic hydroxyl group, there may be used amines of the aliphatic, aromatic or alicyclic series. Among the aliphatic compounds there may be mentioned monoamines, for example, diethylamine, butylamine, hexylamine, dodecylamine, cetylamine, oleylamine, octadecylamine, arachidylamine, behenylamine or mixtures of these monoamines, or polyamines such as ethylene diamine, propylene diamine, triethylene tetramine or the corresponding N-alkyl-polyamines containing alkyl groups having 8 to 22 carbon atoms. There may also be mentioned basic derivatives of such amines, and esters of hydroxy-amines with higher fatty acids, for example, triethanolamine coconut oil fatty acid ester, or partial amides of polyamines with fatty acids, for example, triethylene tetramine monoacylated with coconut oil fatty acid. Among the amines of the aromatic series there may be mentioned above all amines of the benzene or naphthalene series with alkyl side chains containing, for example, 8 to 18 carbon atoms. From the alicyclic series there are advantageously used resin amines, such as abietylarnine, abietyl-methylamine, the amine mixture of tall oil which mixture contains resin amines in addition to higher alkylamines, or hydrogenated ab ietylamine. There may also be used amidines, such as lauric acid or stearic acid amidine.

'For the purpose of this invention suitable products are 2 those obtainable by reacting one molecular proportion of an amine with at least three, for example, 3-20, molecular proportions of an alkylene oxide, for example, the reaction product of one mol of dodecylamine with about six mols of ethylene oxide or of one mol of oleylamine with six, eight or sixteen mols of ethylene oxide, or of one mol of stearylamine with four, eight or sixteen mols of ethylene oxide, the reaction product of a monoalkylpropylene diamine, of which the alkyl group is the radical of tallow fatty acid, with eight mols of ethylene oxide, or the reaction product of a monoalkyl-propylene diamine, of which the alkyl group is unbranched and contains sixteen to eighteen carbon atoms, with six mols of ethylene oxide.

From the above remarks it will be apparent that compounds of the formula are especially suitable for the process of this invention, in which formula R represents an advantageous unbranched aliphatic hydrocarbon radical containing at least 12, and advantageous 16 to 22, carbon atoms, In and n each represent the whole number 1 or 2, and p, q and r represent whole numbers such that the sum p+q+(m-l)(rl) is at least 3 and at most 20.

The corresponding compound-s derived from N-alkyldiethylene triarm'ne are also useful in the process of the present invention.

-If the compounds are prepared from propylene oxide rather than ethylene oxide, they have the formula corresponding otherwise to Formula 2 but containing groups of the composition TOE. instead of the CH -CH O groups.

It will also be apparent that nitrogen compounds of the formula (3) (CHZCH2O)DH (CH2CH2O-)QH are especially suitable for the process, in which formula R represents an advantageously unbranched aliphatic hydrocarbon radical containing at least 12, and advantageously 16 to 20 carbon atoms, and p and q each represent a whole number such that the sum p+q is at least three and advantageously 8 to 16.

Instead of compounds containing free hydroxyalkyl groups, there may be used the acid esters of these hydroxyalkyl-compounds with polybasic acids, for example, phosphoric or sulfuric acid, or the water-soluble salts of these esters, for example, the alkali metal or ammonium salts or amine salts.

The ethylene oxide addition products are made by the methods customary for making such products. They can be made, for example, by reacting the components at a raised temperature. Advantageously the alkylene oxide is added to the amine, not all at once, but gradually by introducing the alkylene oxide, for example, in the gaseous or liquid state, into the amino-compound at a temperature at which the alkylene oxide reacts, for example, at 50200 C. If desired, the reaction may be carried out in a closed vessel under superatmospheric pressure, advantageously at 2 to 10 atmospheres gauge pressure. The reaction mixture may, if necessary, contain a catalyst. As a catalyst there is advantageously used a substance of alkaline reaction, such as metallic sodium, an alkali metal hydroxide or carbonate or an alkali metal salt of a carboxylic acid of low molecular weight.

The condensation products used in the process are soluble or easily dispensible in water. The solubility in Water may, if desired, be increased by introducing groups enhancing solubility in water. Thus, for example, quaternary ammonium salts may be used which contain alkylene glycol chains derived from azfl-alkylene oxides and are obtained, for example, by the additive combination of an alkylating agent with a reaction product of a primary, secondary or tertiary amine of the kind mentioned above with the alkylene oxide. There may be mentioned the quaternary ammonium salt which is obtained by quaternating with dimethyl sulfate the reaction product of oleylamine with 6.to 10 molecular proportions of ethylene oxide.

Instead of reaction products of alkylene oxide with primary, secondary or tertiary amines of the kind mentioned above, there may be used products which are obtained by introducing into the amines polyglycol ether chains having the appropriate number of ether groups.

The process of the invention is equally advantageous in dyeing or printing. In dyeing from aqueous baths the proportion of the substances to be added thereto may vary with-in relatively wide limits. The proportions of the dyesuif depends, of course, on the strength of the dyeing desired. It is of advantage to adjust the proportion of the nitrogenous compound relatively to the proportion of the dyestufi so that the ratio of the said compound to dyestufi is within the range of about 1:8 to 1:2. Advantageously the proportion of the nitrogenous compound is about A of the proportion of the dyestufi.

The proportion of the nitrogenous compound-should amount to at least 0.25 percent calculated on the weight of the fibers, even when pale dyeings are to be produced, for which less than 1 percent of 'dyestuif calculated on the weight of the fiber is used.

Furthermore, it has been found'advantageous to dye in an acid medium, the pH of the dyebath being maintainedbetween 3 and 6, preferably between 4 and 5; this pH value is advantageously adjusted by adding acetic acid or, if desired, formic or sulfuric acid. It is also of advantage to add sodium sulfate to the dyebath. i

As is the general practice when dyeing wool, dyeing is carried out at an elevated temperature, advantageously so that the actual dyeing process is initiated at about 50 to 80 C., the temperature is then raised to the boil, and dyeing is continued and terminated at the boil. It has, however, been observed that it is not at all necessary to raise the temperature close to, or actually to, the boiling point of the dyebafli. As a rule, practically equally good results are obtained when the dyeing process is performed below the boil, for example at a temperature from 80 to 90 C.

To ensure that the nitrogenous compound acts reliably from the outset, it is advisable to immerse the material in the dyebath (which contains the acid, if desired sodium sulfate, and the auxiliary) at room temperature or at most at a slightly higher temperature, then to raise the temperature of the dyebath and to add the dyestuff in Example 1 100 parts of knitting wool, 3000 parts of water, 10 parts of crystalline sodium sulfate, 6 parts of acetic acid of 40% strength and 0.5 part of the addition product of oleylamine and ethylene oxide described below are heated to 80 C. A solution of 2 parts of the dyestufl of the formula OH Cl the form of an aqueous solution at an elevated temperature, for example at 50 to 80 C.

As is known, the dyestuffs to be used in the present process are suitable above all for dyeing and printing cellulosic materials by special methods, although some of them have also been proposed for dyeing wool. A large number of these dyestulls are not very suitable or even quite unsuitable for dyeing wool because they produce not only very patchy and above all weak dyeings but also are absorbed very slowly by the material.

It is in fact known that the levelling capacity of wool dyestuffs of poor levelling capacity can be improved by adding addition products of ethylene oxide with certain hydroxy or amino compounds, but these dyestuffs depend for their suitability for dyeing wool on the normal process of absorption and contain no groups capable of reacting with the fibrous material. t is very surprising that with the dyestuffs to be used in the present processwhich are capable of reacting with the fibrous material in a reaction which is fundamentally difierent from the process involved in dyeing with acid dyestuffs that do not cont in reactive substituents-the addition of the nitrogenous compound produces the effect of considerably accelerating the absorption and substantially improving the possible exhaustion of the dyebath so that with otherwise unsuitable dyestuffs very valuable level dyeings are obtained which are distinguished by excellent fastness properties and in general by particularly pure tints.

The present process is also very suitable for printing worsted tops by the slubbing method. The printing pastes used for this purpose contain in addition to at least one dyestufi and an auxiliary of the composition defined above, a thickener such as tragacanth or British gum, and they contain advantageously also an acid, for example acetic acid. They may further contain other additives conventionally incorporated with printing pastes, such as turpentine, hydrotropic substances such as urea and/ or agents capable of preventing reduction, such as sodium nitrobenzene sulfonate.

In other respects the procedure conventionally employed in slubbing printing may be followed. The printed material is steamed for 40 to 120 minutes, for example under atmospheric pressure, advantageously with at least one interruption.

The slubbing prints obtained in this manner are distinguished by a good yield and very good fastness properties, more especially good pott ng stability, fastness to over-printing with acid dyestuffs and to water spotting.

The general practice adopted in direct-printing Woolen piece-goods and wool yarns requires the Wool to be HO3S -NH([3 l--NH in a small amount of water is added to this dyebath. The bath is raised to the boil within /2 hour, and dyeing is carried out for 1 hour at the boil. The wool is then rinsed and dried. A very pure scarlet dyeing is obtained. When the ethylene oxide addition product is omitted, a skittery, weak, practically useless dyeing is obtained.

The ethylene oxide adduct is prepared thus:

parts of commercial oleylarnine are mixed with 1 part or: finely distributed sodium and heated to 140 C., whereupon ethylene oxide is introduced at 135l40 C. When the ethylene oxide is being consumed rapidly, the reaction temperature is reduced to to C., and the introduction of ethylene oxide is continued until 113 parts thereof have been absorbed. The reaction product obtained in this manner gives an almost clear solution in water.

-Example 2 100 parts of worsted tops, 2000 parts of water, 4 parts of acetic acid of 40% strength and 0.2 5 part of the ethylene oxide addition product described in the last paragraph of Example 1 are heated to 60 C. A solution of 3 parts of the dyestutl of the formula N R i r t O N N HO S- SO3H Cl is used.

A practically identical dyeing is obtained when, after addition of the dyestuff, the temperature is raised to only 85 C. and dyeing is carried out at this temperature for 1 hour.

Example 3 A dyebath is prepared finom 4000 parts of water, parts of acetic acid of 40% strength, parts of crystalline sodium sulfate, 0.25 part of the ethylene oxide addition product described in the last paragraph of Example 1 and 2 parts of the dyestufi of the formula At 60 C. 100 parts of woollen piece-goods are immersed in this dyebath, the temperature is raised to the boil within /2 hour, and dyeing is carried out for 1 hour at the boil. The material is then rinsed and dried. A level blue dyeing is obtained. When the ethylene oxide addition product is emitted, a skittery, patchy, commercially useless dyeing results.

Example 4 With the use of the dyestufi of formula (6) a printing paste is prepared fiOHI I 30 parts of dyestutf 50 parts of urea 180 parts of tragacanth thickening 60:1000

25 parts of the ethylene oxide adduct described in the last paragraph of Example 1 parts of acetic acid of 80% strength parts of turpentine 680 parts of water 1000 parts With this printing paste a conventional slubbing print is produced on worsted tops. The printed wool is then steamed for 45 minutes under atmospheric pressure, then rinsed for 45 minutes on each occasion with water of 40 C. and with Water of 80 C., and finished in the usual manner. a

The red slubbing print produced in this manner is distinguished by very good fastness properties, above all by its potting fastness, fastness to over-printing With acid dyestuffs and to water spotting.

Instead of the dyestufi of Formula 6 the following dyestuffs may be used:

(a) The dyestufi obtained by condensing 1 mol of copper phthalocyanine tetrasulfonyl chloride with 1-2 mols of the compound of the formula (b) The dyestufl of the formula Example 5 A dyebath is prepared from 4000 parts of water, 5

parts of acetic acid of 40% strength, 0.5 part of a reaction product from octadecylamine and 4 mols of ethylene oxide, and 2 parts of the dyestutl' of Formula 5. At

C. 100 parts of Woollen piece-goods are immersed in this dyebath which is then raised to the boil'within /2 hour, and dyeing is carried out at the boil for 1 hour.

The material is then rinsed and dried. A level, deep red dyeing is obtained.

The reaction product from ootadecylarnine and 4 mols of ethylene oxide used above may be replaced by any one of the following adducts of ethylene oxide:

(a) N-alkyl-propylenediamine (alkyl radicals=radicals of tallow fatty acids) and 8 mols of ethylene oxide;

(b) N-alkyl-propylenediamine or N alkyl ethylenediamine (alkyl radicals: straight-chain and saturated, containing 16 to 18 carbon atoms) and 6 mols of ethylene oxide;

(0) mixtureof behenylamine and arachidylamine 8 to 20 mols of ethylene oxide;

(d) mixture of the amines obtained by reducing the tall-ow fatty acid amides 6 to 8 mols of ethylene oxide;

(e) N-dodecyl-propylenediarnine and 6 mols of ethylene oxide;

(f) Dodecylamine and 3 mols of ethylene oxide;

(g) Dodecylamine and 3 mols of propylene oxide. This propylene oxide addition product is obtained in the following manner:

24 parts of commercial dodecylarnine are heated in the presence of 0.13 pant of finely distributed sodium to 160 C. in a current of nitrogen. Propylene oxide gas is then introduced until 19.5

a parts thereof have been absorbed.

(h) N-octadecyl-diethylenetrianiine and 15 -to 20 mols o ethyleneoxide.

Example 6 A dyebath is prepared from 4000 parts of water, 5 parts of acetic acid of 40% strength, 0.5 part of the ethylene oxide addition product described in the last paragraph of Example 1 and 2 parts of the dyestnfi of the formula At 60 C. 100 parts of woollen piece-goods are immersed in this dyebath which is then raised to the boil within /2 hour, and dyeing is carried out for 1 hour at the boil. The material is then rinsed and dried. A level red dyeing results. 7

When dyeing is carried out at C. instead of at the boil, level tints are likewise obtained.

Example 7 A dyebath is prepared from 4000 parts of water, 6

(Red) parts of acetic acid of 40% strength, 2 parts of the dyestuff of Formula 5 and 1 part of an auxiliary prepared as described under ((1) below. At 50. C., parts of woollen piece-goods are immersed in this dyebath which is then gradually raised to the boil. The wool is dyed for 1 hour at the boil, rinsed in cold water and dried. A pure red, level dyeing results. When the auxiliary is omitted, the resulting dyeing is skittery and practically useless. v

A similarly good levelling effect is achieved when Wool is dyed in the above manner with the use of the auxiliary mentioned and of the dyestufi of Formula 7.

The dyeing assistant is prepared in the following man- Example 8 A printing paste is prepared from:

parts of dyestufi of Formula 6 200 parts of urea (a) 79 parts (0.3 mol) of a mixture of fatty amines 509 Parts Of gj f thlckenmg 3011000 consisting of 30% of hexadecylarnine, 25% octadecyl- 69 Parts Of acetlcflcld 0f Strength amine and of octadecenylarnine are reacted with 15 parts of the ethylene OXlde adduct descrlbed m h ethylene oxide in the presence of 0.8 part of sodium until 13st p p of f p 1 106 parts (2.4 mols) of ethylene oxide have been ab- 10 10 parts sodlum meta-mtrobenzenesulfonate sorbed. 185 parts of water At the start the reaction temperature is 140 to 150 C. 1000 parts and can be reduced gradually to to C.

30.75 parts (0.05 mol) of the resulting ethylene oxide A piece of unchlorinatcd woven Wool fabric is printed addition product are mixed in a stirring flask at 60 C. 1 with this paste in the conventional manner, and then within 15 minutes with 5.4 parts of urea and then within steamed for 15 minutes in a star steamer or in a con- 30 minutes with 5.4 parts of sulfamic acid (0.05 tinuous steamer, rinsed in Water and finished as usual. mol+10%), and the Whole is heated for 5 to 6 hours A strong, level, red print is obtained. Without the ethyl on a boiling water bath under nitrogen. ene oxide addition product the print is tinctorially weak,

The resulting product (41 parts) is readily soluble in 2Q Skittery and unfit for practical use. water and of neutral reaction. What is claimed is:

Similar results are obtained by dyeing wool as de- 1. A process for dyeing Wool with acid dyestu f scribed in the first paragraph of this example, with the which comprises treating the Wool in an aqueous medium exception that the auxiliary prepared as described under with a dyestufi which contains at least three sulfonic (a) above is replaced by any one of the auxiliaries pre- 25 acid groups and is capable of entering into chemical compared as described below: bination with the wool, and carrying out the treatment (b) 31.2 parts of urea and 27.6 parts (about 0.17 mol) in the presence of a compound which corresponds to the of urea phosphate are mixed and heated in a flask. Above formula TCk-rHn-r 1 1 m 1 70 C., the mixture is raised with stirring within 1 to in which R represents an aliphatic hydrocarbon radical 1 /2 hours to 155 C., maintained for 30 minutes at 155 I containing at least 12 and at the most 22 carbon atoms, to 160 C. and then allowed to cool to about C. k, m, n, p, q and r each represent a whole number, k, 49.2 parts (0.08 mol) of the ethylene oxide adduct m and 11 each being at the most 2 and the sum described under (a) above are then added, and the whole p-i-q-l-(ml)(r1) being at least 3 and at the most 20. is heated for 2 hours at to C. under nitrogen 2. A process for dyeing Wool with acid dy'estufis, cooled to 110 C., mixed with Water and the final weight r which comprises treating the Wool in an aqueous medium is adjusted to 196 parts, to yield a clear solution of neutral With a dyestufi which contains at least three sulfonic acid reaction (of 25% strength, calculated from the ethylene groups and is capable of entering into chemical combinaoxide adduct used). tion with the Wool, and carrying out the treatment in (c) 79 parts of the mixture of fatty amines mentioned the presence of an ester of an at least dibasic acid and under (a) above are reacted as described above with ahydroxy compound of the formula ethylene oxide in the presence of 0.8 part of sodium 70 in which R represents an aliphatic hydrocarbon radical until 53 parts of ethylene oxide have been absorbed.

43.8 parts (0.1 mol) of the resulting ethylene oxide adduct are reacted as described under (a) above with 10.75 parts of urea and 10.75 parts of sulfarnic acid; final weight: 64.9 parts.

containing at least 12 and at the most 22 carbon atoms,

k, m, n, p, q and 1' each represent a whole number, k, m

and 11 each being at the most 2 and the sum being at least 3 and at the most 20.

5. A process for dyeing wool with acid dyestuffs, which comprises treating the wool in an aqueous medium with a dyestuif which contains at least three sulfonic acid groups and a chloro-lz3z5-triazine radical and carrying out the treatment in the presence of a compound of the containing at least 12 and at the most 22 carbon atoms, k, m, n, p, q and r, each represent a Whole number, k, m and it each being at the most 2 and the sum p+q+( being at least 3 and at the most 20.

4. A process for dyeing Wool With acid dyestufis, which comprises treating the Wool in an aqueous medium with a dyestufi which contains at least three sulfonic acid groups and at least one reactive halogen atom and carrying out the treatment in the presence of an ester of an at least dibasic acid and a hydroxy compound of the formula in which R represents an aliphatic hydrocarbon radical containing at least 12 and at the most 22 carbon atoms, k, in, n, p, q and r each represent a whole number, k, m and it each being at the most 2 and the sum P+q+( being at least 3 and at the most 20.

6. A process for dyeing wool With acid dyesttnfs, which comprises treating the Wool in an aqueous medium with a dyestuff which contains at least three sulfonic acid groups and a chloro-1z3z5-t-riazine radical and carrying out the treatment in the presence of an ester of an at containing at least 12 and at the most 22 carbon atoms, k, m, n, p, q and r each represent a Whole number, k, 70 m and 11 each being at the most 2 and the sum eing at least 3 and at the most 20. 75

in which R represents an aliphatic hydrocarbon radical containing at least 12 and at the most 22 carbon atoms, k, m, n, p, q and r each represent a Whole number, k, m and n each being at the most 2 and the sum being at least 3 and at the most 20.

13 14 7. A process for dyeing wool in the slubbing printing carbon atoms, and p and q each represent whole numbers, process with acid dyestuffs, which comprises treating the the sum p+q being at least 3 and at the most 20. wool in an aqueous medium with a dyestutf which con- 9. A process for dyeing wool with acid dyestufis, which tains at least three sulfonic acid groups and a chlorocomprises treating the wool in an aqueous medium with 1:3:5-triazine radical and carrying out the treatment in a dyestnft which contains at least three sulfonic acid the presence of a compound of the formula groups and is capable of entering into chemical combina- (|3H(]3H O H n I- Ck1 2r-1 R-N (0H,) N\ I c n-( :H o H IIH(IJH 0 H H J k 1 2k 1 r 1 m 1 in which R represents an aliphatic hydrocarbon radical tion with the wool, and carrying out the treatment in the containing at least 12 and at the most 22 carbon atoms, presence of an addition product of one molecular prok, m, n, p, q and r each represent a whole number, k, m portion of oleylamine and about 6 to 9 molecular proand n each being at the most 2 and the sum portions of ethylene oxide.

10. A process for dyeing wool with acid dyestufls, 25 which comprises treating the wool in an aqueous medium being at least 3 and at the most 20. with a dyestufi which contains at least three sulfonic acid A Process for dyeing W001 Wlth aciddyestufis, which groups and is capable of entering into chemical combinacomprises treating the Wool in an aqueous medium with 8. tion with the wool, and carrying out the treatment in the dyestufi which contains at least three sulfonic acid groups re ence of an addition product of one molecular proand is capable of entering into chemical combination portion of N-alkyl-propylenediamines, the :alkyl radicals with the wool, and carrying out the treatment in the presof which are the same as those of tallow fatty acids, and ence of a compound which corresponds to the formula about 8 molecular proportions of ethylene oxide.

H H References Cited in the file of this patent UNITED STATES PATENTS 1,970,578 Schoeller et a1. Aug. 21, 1934 2,214,067 Petersen Sept. 10, 1940 2,773,871 Brassel et a1 Dec. 11, 1956 in which R represents an unbranched aliphatic hydrocar- 2,863,875 Bienert et al. Dec. 9, 1958 'bon radical containing at least 12 and at the most 22 40 2,940,812 Denyer et al June 14, 1960 

1. A PROCESS FOR DYEING WOOL WITH ACID DYESTUFFS, WHICH COMPRISES TREATING THE WOOL IN AN AQUEOUS MEDIUM WITH A DYESTUFF WHICH CONTAINS AT LEAST THREE SULFONIC ACID GROUPS AND IS CAPABLE OF ENTERING INTO CHEMICAL COMBINATION WITH THE WOOL, AND CARRYING OUT THE TREATMENT IN THE PRESENCE OF A COMPOUND WHICH CORRESPONDS TO THE FORMULA 